EP1274574A1 - Feuille de polyester transparente, scellable, traitee pour retarder la combustion et stabilisee aux uv, son procede de fabrication et son utilisation - Google Patents

Feuille de polyester transparente, scellable, traitee pour retarder la combustion et stabilisee aux uv, son procede de fabrication et son utilisation

Info

Publication number
EP1274574A1
EP1274574A1 EP01900408A EP01900408A EP1274574A1 EP 1274574 A1 EP1274574 A1 EP 1274574A1 EP 01900408 A EP01900408 A EP 01900408A EP 01900408 A EP01900408 A EP 01900408A EP 1274574 A1 EP1274574 A1 EP 1274574A1
Authority
EP
European Patent Office
Prior art keywords
film
polyester film
film according
layer
polyester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP01900408A
Other languages
German (de)
English (en)
Other versions
EP1274574B1 (fr
Inventor
Ursula Murschall
Ulrich Kern
Andreas Stopp
Günther Crass
Herbert Peiffer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Polyester Film GmbH
Original Assignee
Mitsubishi Polyester Film GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Polyester Film GmbH filed Critical Mitsubishi Polyester Film GmbH
Publication of EP1274574A1 publication Critical patent/EP1274574A1/fr
Application granted granted Critical
Publication of EP1274574B1 publication Critical patent/EP1274574B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/91—Product with molecular orientation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
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    • Y10T428/2495—Thickness [relative or absolute]
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    • Y10T428/2495—Thickness [relative or absolute]
    • Y10T428/24959—Thickness [relative or absolute] of adhesive layers
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    • Y10T428/24975—No layer or component greater than 5 mils thick
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    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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    • Y10T428/259—Silicic material
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    • Y10T428/2813—Heat or solvent activated or sealable
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    • Y10T428/2817—Heat sealable
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    • Y10T428/2826—Synthetic resin or polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2922—Nonlinear [e.g., crimped, coiled, etc.]
    • Y10T428/2924—Composite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y10T428/2942—Plural coatings
    • Y10T428/2947—Synthetic resin or polymer in plural coatings, each of different type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
    • Y10T428/2967—Synthetic resin or polymer
    • Y10T428/2969—Polyamide, polyimide or polyester
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31565—Next to polyester [polyethylene terephthalate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31616—Next to polyester [e.g., alkyd]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31616—Next to polyester [e.g., alkyd]
    • Y10T428/3162—Cross-linked polyester [e.g., glycerol maleate-styrene, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]

Definitions

  • the invention relates to a transparent, UV-stabilized and flame-retardant, sealable, biaxially oriented polyester film consisting of at least one base layer B and cover layers A and C applied to both sides of this base layer.
  • the film additionally contains at least one UV stabilizer as light stabilizer and at least one flame retardant ,
  • the invention further relates to a method for the production of the film and its use.
  • the films are particularly suitable for outdoor applications, such as for greenhouses, canopies. Furthermore, the films are very suitable for covering and thus for protecting metallic surfaces on which the films can be heat-sealed. In outdoor applications, films that do not contain UV-absorbing materials show yellowing and a deterioration in the mechanical properties due to photooxidative degradation by sunlight after a short time. In addition, the films and articles made from them are particularly suitable for applications in which fire protection or flame retardancy is required.
  • Sealable, biaxially oriented polyester films are known in the prior art. Sealable, biaxially oriented polyester films which are equipped with one or more UV absorbers are also known. These films, which are known from the prior art, are distinguished either by good sealing behavior, good optics or by acceptable processing behavior.
  • GB-A 1 465 973 describes a coextruded, two-layer polyester film, the one layer of which contains isophthalic acid and copolyesters containing terephthalic acid and the other layer of which consists of polyethylene terephthalate. There is no usable information about the sealing behavior of the film. Due to the lack of pigmentation, the film cannot be produced reliably, ie cannot be wound and can only be processed to a limited extent.
  • EP-A 0035835 describes a coextruded sealable polyester film which, in order to improve the winding and processing behavior in the sealing layer, contains particles whose average particle size exceeds the layer thickness of the sealing layer.
  • the particulate additives form surface protrusions that prevent the unwanted blocking and sticking of the film on rollers or guides.
  • No further details regarding the incorporation of antiblocking agents are given about the other, non-sealable layer of the film. It remains open whether this layer contains antiblocking agents.
  • the choice of particles with a larger diameter than the thickness of the sealing layer and at the concentrations given in the examples deteriorates the sealing behavior of the film.
  • No information is given on the sealing temperature range of the film.
  • the seal seam strength is measured at 140 ° C and is in a range from 63 to 120 N / m (0.97 N / 15 mm to 1.8 N / 15 mm film width).
  • EP-A 0 432 886 describes a coextruded multilayer polyester film which has a first surface on which a sealable layer is arranged and which has a second surface on which an acrylate layer is arranged.
  • the sealable cover layer can also consist of copolyesters containing isophthalic acid and terephthalic acid.
  • the film on the back has improved processing properties. No information is given on the sealing temperature range of the film.
  • the seal seam strength is measured at 140 ° C.
  • a seal seam strength of 761.5 N / m (11.4 N / 15 mm) is specified for an 11 ⁇ m thick seal layer. adversely on the back acrylic coating is that this side no longer seals against the sealable top layer.
  • the film can therefore only be used to a very limited extent.
  • EP-A 0 515 096 describes a coextruded, multi-layer sealable polyester film which contains an additional additive on the sealable layer.
  • the additive can e.g. contain inorganic particles and is preferably applied in an aqueous layer to the film during its manufacture. As a result, the film should maintain the good sealing properties and be easy to process. The back contains very few particles that get into this layer mainly through the regranulate. No information is given in this document on the sealing temperature range of the film.
  • the seal seam strength is measured at 140 ° C and is more than 200 N / m (3 N / 15 mm). A seal seam strength of 275 N / m (4.125 N / 15 mm) is given for a 3 ⁇ m thick sealing layer.
  • WO 98/06575 describes a coextruded multilayer polyester film which contains a sealable cover layer and a non-sealable base layer.
  • the base layer can be constructed from one or more layers, the interior of the layers being in contact with the sealable layer.
  • the other (outer) layer then forms the second non-sealable cover layer.
  • the sealable top layer can consist of copolyesters containing isophthalic acid and terephthalic acid, which, however, contain no antiblocking particles.
  • the film also contains at least one UV absorber, which is added to the base layer in a weight ratio of 0.1 to 10%. Triazines, for example ® Tinuvin 1577 from Ciba, are preferably used as UV absorbers.
  • the base layer is equipped with common antiblocking agents.
  • the film is characterized by a good sealability, but does not have the desired processing behavior and also has deficits in the optical properties, such as gloss and cloudiness.
  • DE-A 2346787 describes a flame-retardant raw material. In addition to the raw material, the use of the raw material for the production of films and fibers is also described. The following deficits are evident when using this phospholane-modified raw material in film production
  • the raw material mentioned is sensitive to hydrolysis and must be predried very well. When drying the raw material with dryers which correspond to the prior art, the raw material sticks together, so that a film can only be produced under the most difficult conditions. -
  • the films produced in this way under uneconomical conditions become brittle when exposed to temperature, i.e. H. the mechanical properties deteriorate due to the embrittlement, so that the film is unusable. This embrittlement occurs after 48 hours of exposure to heat.
  • the regenerate which is inherently obtained in a concentration of up to 60% by weight, based on the total weight of the film, without the physical properties of the film being adversely affected.
  • the film Since the film is intended in particular for outdoor use and / or critical indoor use, it should have a high UV stability.
  • a high UV stability means that the films are not or only extremely little damaged by sunlight or other UV radiation.
  • the films should not yellow over several years of outdoor use, should not show any embrittlement or cracking on the surface, and should also have no deterioration in the mechanical properties.
  • High UV stability means that the film absorbs the UV light and only lets light through in the visible range.
  • a flame-retardant effect means that the transparent film meets the conditions according to DIN 4102 Part 2 and in particular the conditions according to DIN 4102 Part 1 in a so-called fire protection test and can be classified into building material classes B 2 and especially B1 of the flame-retardant materials.
  • the film should pass the UL test 94 (Vertical Burning Test for Flammability of Plastic Material) so that it can be classified in class 94 VTM-0. This means that the film no longer burns 10 seconds after the Bunsen burner has been removed, no glowing is observed after 30 seconds and no dripping is found.
  • UL test 94 Vertical Burning Test for Flammability of Plastic Material
  • Economic production includes the fact that the raw materials or the raw material components required for producing the flame-retardant film can be dried using industrial dryers which meet the standard of technology. It is essential that the raw materials do not stick together and are not thermally broken down.
  • industrial dryers include vacuum dryers, fluidized bed dryers, fluid bed dryers and fixed bed dryers (shaft dryers). These dryers operate at temperatures between 100 and 170 ° C. at which the flame-retardant raw materials mentioned in the prior art stick together, so that film production is not possible.
  • the film raw material goes through a temperature range of approx. 30 ° C to 130 ° C at a vacuum of 50 mbar. After that, a so-called drying in a hopper at temperatures of 100 - 130 ° C and a residence time of 3 to 6 hours is required. Even here the raw material mentioned sticks extremely.
  • No embrittlement under thermal stress means that the film has no embrittlement and no disadvantageous mechanical properties after 100 hours of annealing at 100 ° C. in a forced air oven.
  • the good mechanical properties include a high modulus of elasticity (E MD > 3200 N / mm 2 ; E- ⁇ > 3500 N / mm 2 ) and good tensile strength values (in MD> 100 N / mm 2 ; in TD> 130 N / mm 2 ).
  • the object is achieved according to the invention by providing a flame-retardant, UV-stabilized, biaxially oriented, sealable polyester film with at least one base layer B, a sealable cover layer A and a further cover layer C located on the other side of the base layer B, the sealable layer Cover layer A preferably has a seal initiation temperature of less than 110 ° C. and preferably a seal seam strength of at least 1.3 N / 15 mm, and the film contains at least one UV absorber or mixtures of different UV absorbers and at least one flame retardant or mixtures of different flame retardants.
  • the UV stabilizer is expediently metered in directly as a masterbatch in film production, the concentration of the UV stabilizer preferably between 0.01% by weight and 5% by weight, based on the weight of the layers containing the UV absorber.
  • the flame retardant contained in the film according to the invention is preferably metered in directly during film production using the so-called masterbatch technology, the concentration of the flame retardant being between 0.5 and 30% by weight, preferably between 1 and 20% by weight, based on the weight of the layers containing the flame retardant is.
  • the film is preferably three-layered and then comprises as layers the base layer B, the sealable cover layer A and the non-sealable cover layer C.
  • the film according to the invention can have additional intermediate layers.
  • the base layer B of the film consists of a thermoplastic, preferably at least 90% by weight of a thermoplastic polyester.
  • a thermoplastic polyester preferably at least 90% by weight of a thermoplastic polyester.
  • polyesters which consist of at least 90 mol%, in particular at least 95 mol%, of ethylene glycol and terephthalic acid units or of ethylene glycol and naphthalene-2,6-dicarboxylic acid units.
  • the remaining monomer units come from other aliphatic, cycloaliphatic or aromatic diols or dicarboxylic acids, as can also occur in layer A and / or layer C.
  • Suitable other aliphatic diols are, for example, diethylene glycol, triethylene glycol, aliphatic glycols of the general formula HO- (CH 2 ) n -OH, where n represents an integer from 3 to 6 (in particular propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol and hexane-1,6-diol) or branched aliphatic glycols with up to 6 carbon atoms.
  • cyclohexanediols in particular cyclohexane-1,4-diol
  • Suitable other aromatic diols correspond, for example, to the formula HO-C 6 H 4 -XC 6 H 4 -OH, where X is -CH 2 -, - C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -O -, -S- or -SO 2 - stands.
  • bisphenols of the formula HO-C 6 H 4 -C 6 H 4 -OH are also very suitable.
  • aromatic dicarboxylic acids are preferably benzenedicarboxylic acids, naphthalene dicarboxylic acids (for example naphthalene-1, 4- or 1,6-dicarboxylic acid), biphenyl-x, x'-dicarboxylic acids (in particular biphenyl-4,4'-dicarboxylic acid), diphenylacetylene-x, x ' -dicarboxylic acids (especially diphenylacetylene-4,4'-dicarboxylic acid) or stilbene-x, x'-dicarboxylic acids.
  • naphthalene dicarboxylic acids for example naphthalene-1, 4- or 1,6-dicarboxylic acid
  • biphenyl-x, x'-dicarboxylic acids in particular biphenyl-4,4'-dicarboxylic acid
  • diphenylacetylene-x, x ' -dicarboxylic acids especially diphenylacetylene
  • cyclohexanedicarboxylic acids (in particular cyclohexane-1,4-dicarboxylic acid) should be mentioned.
  • aliphatic dicarboxylic acids the (C 3 -C 19 ) alkanedioic acids are particularly suitable, the alkane fraction being straight-chain or branched.
  • polyesters according to the invention can e.g. according to the transesterification process.
  • the starting point is dicarboxylic acid esters and diols, which are mixed with the usual transesterification catalysts, such as zinc, calcium, lithium,
  • Antimony trioxide or titanium salts polycondensed.
  • the production can just as well be carried out after the d a re ktv e re s t e ru n g s v a r re n i n G e g e n w a r t v o n
  • the sealable cover layer A applied to the base layer B by coextrusion is based on polyester copolymers and consists essentially of copolyesters which are composed predominantly of isophthalic and terephthalic acid units and of ethylene glycol units. The remaining monomer units come from other aliphatic, cycloaliphatic or aromatic diols or dicarboxylic acids, as can also occur in the base layer.
  • the preferred copolyesters are those composed of ethylene terephthalate and ethylene isophthalate units.
  • the proportion of ethylene terephthalate is preferably 40 to 95 mol% and the corresponding proportion of ethylene isophthalate 60 to 5 mol%.
  • Particularly preferred are copolyesters in which the proportion of ethylene terephthalate is 50 to 90 mol% and the corresponding proportion of ethylene isophthalate is 50 to 10 mol% and very particularly preferred are copolyesters in which the proportion of ethylene terephthalate is 60 to 85 mol% and the corresponding proportion of ethylene isophthalate is 40 to 15 mol%.
  • the same polymers as described above for the base layer B can be used for the other, non-sealable top layer C or for any intermediate layers that are present.
  • the desired sealing and processing properties of the film according to the invention are obtained from the combination of the properties of the copolyester used for the sealable cover layer and the topographies of the sealable cover layer A and the non-sealable cover layer C.
  • the seal initiation temperature of preferably less than 110 ° C. and the seal seam strength of preferably at least 1.3 N / 15 mm are achieved if the copolymers described in more detail above are used for the sealable cover layer A.
  • the best sealing properties of the film are obtained if no further additives, in particular no inorganic or organic fillers, are added to the copolymer. In this case, you get the given copolyester lowest sealing starting temperature and highest sealing seam strengths.
  • the handling of the film is worse in this case, since the surface of the sealable cover layer A tends to block.
  • the film can hardly be wrapped and is hardly suitable for further processing on high-speed packaging machines. In order to improve the handling of the film and the processability, it is necessary to modify the sealable cover layer A.
  • the roughness of the sealable top layer characterized by the R a value, should be less than 30 nm. In the other case, the sealing properties are negatively influenced in the sense of the present invention.
  • the measured value of the gas flow should be in the range of 500-4000 s. At values below 500 s, the sealing properties are negatively influenced in the sense of the present invention, and at values above 4000 s, the handling of the film becomes poor.
  • the topography of the non-sealable cover layer C should be characterized by the following set of parameters:
  • the coefficient of friction (COF) of this side against itself should be less than 0.5. Otherwise the winding behavior and further processing of the film are unsatisfactory.
  • the roughness of the non-sealable top layer should be greater than 40 nm and less than 100 nm. Values smaller than 40 nm have a negative impact on the film's processing and processing behavior and values larger than 100 nm impair the optical properties (gloss, haze) of the film.
  • the measured value of the gas flow should be in the range below 120 s. At values above 1 20 s, the winding and processing behavior of the film is adversely affected.
  • UV stabilizers which are suitable for incorporation into polyesters can be selected for UV stabilization of the film according to the invention.
  • suitable UV stabilizers are known in the art and e.g. described in more detail in WO 98/06575, in EP-A-0 006 686, in EP-A-0 031 202, EP-A-0 031 203 or in EP-A-0 076 582.
  • Light especially the ultraviolet portion of solar radiation, i.e. H. the wavelength range from 280 to 400 nm initiates degradation processes in thermoplastics, as a result of which not only the visual appearance changes as a result of color change or yellowing, but also the mechanical-physical properties are adversely affected.
  • Polyethylene terephthalates begin to absorb UV light below 360 nm, their absorption increases considerably below 320 nm and is very pronounced below 300 nm. The maximum absorption is between 280 and 300 nm.
  • UV stabilizers or UV absorbers as light stabilizers are chemical compounds that can intervene in the physical and chemical processes of light-induced degradation. Soot and other pigments can partially protect against light. However, these substances are unsuitable for transparent films because they lead to discoloration or color change. For transparent, matt films, only organic and organometallic compounds are suitable which give the thermoplastic to be stabilized no or only an extremely small color or color change, i.e. H. which are soluble in the thermoplastic.
  • UV stabilizers suitable as light stabilizers for the purposes of the present invention are UV stabilizers which absorb at least 70%, preferably 80%, particularly preferably 90%, of the UV light in the wavelength range from 180 nm to 380 nm, preferably 280 to 350 nm. These are particularly suitable if they are thermally stable in the temperature range from 260 to 300 ° C, ie they do not decompose and do not lead to outgassing.
  • Suitable UV stabilizers as light stabilizers are, for example, 2-hydroxybenzophenones, 2-hydroxybenzotriazoles, organochlorine compounds, salicylic acid esters, cinnamic acid ester derivatives, resorcinol monobenzoates, oxalic acid anides, hydroxybenzoic acid esters, sterically hindered amines and triazineziazines, the 2-hydroxylsiazines, the hydroxylsiazines, the 2-hydroxyziazines, the hydroxylsiazines being the 2-hydroxyziazines, the hydroxylsiazines being the 2-hydroxyziazines, the hydroxylsiazines, the 2-hydroxyziazines, the hydroxylsiazines being the 2-hydroxyazoles, are preferred.
  • the film according to the invention contains 0.01% by weight to 5.0% by weight of 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- ( hexyl) oxyphenol of the formula
  • mixtures of these two UV stabilizers or mixtures of at least one of these two UV stabilizers with other UV stabilizers can also be used, the total concentration of light stabilizer preferably being between 0.01% by weight and 5.0% by weight. -%, based on the weight of crystallizable polyethylene terephthalate.
  • the UV stabilizer is preferably contained in the non-sealable top layer C.
  • the base layer B and / or the sealable cover layer A and / or any intermediate layers which may be present can also be equipped with UV stabilizers as required.
  • the concentration of the stabilizer or stabilizers relates to the weight of the layers which are equipped with UV stabilizers.
  • the films according to the invention generally have no yellowing, no embrittlement, no loss of gloss on the surface, no cracking on the surface and no deterioration in the mechanical properties.
  • the light stabilizer can expediently be metered in at the thermoplastic raw material manufacturer or be metered into the extruder during film production.
  • the addition of the light stabilizer via the material batch technology is particularly preferred.
  • the light stabilizer is dispersed in a solid carrier material.
  • the polyester itself or other polymers which are sufficiently compatible with it can be used as the carrier material.
  • the grain size and the bulk density of the masterbatch is similar to the grain size and the bulk density of the polyester, so that a homogeneous distribution and thus a homogeneous UV stabilization can take place.
  • the film according to the invention contains at least one flame retardant which is metered in directly during film production using the so-called masterbatch technology, the concentration of the flame retardant being in the range from 0.5 to 30.0% by weight, preferably from 1.0 to 20.0 wt .-%, based on the weight of the layer of crystallizable thermoplastic, is.
  • a ratio of flame retardant to thermoplastic in the range from 60 to 40% by weight to 10 to 90% by weight is generally maintained in the production of the masterbatch.
  • Typical flame retardants include bromine compounds, chlorinated paraffins and other chlorine compounds, antimony trioxide, aluminum trihydrates, the halogen compounds being disadvantageous because of the halogen-containing by-products formed. Furthermore, the low light resistance of a film equipped with it, in addition to the development of hydrogen halide in the event of fire, is extremely disadvantageous.
  • Suitable flame retardants which are used according to the invention are, for example, organic phosphorus compounds such as carboxyphosphinic acids, their anhydrides and dimethyl methylphosphonate. It is essential to the invention that the organic phosphorus compound is soluble in the thermoplastic, since otherwise the required optical properties are not met. Since the flame retardants generally have a certain sensitivity to hydrolysis, the additional use of a hydrolysis stabilizer can be useful.
  • Phenolic stabilizers, alkali metal / alkaline earth stearates and / or alkali metal / alkaline earth metal carbonates are generally used as hydrolysis stabilizers in quantities of 0.01 to 1.0% by weight. Phenolic stabilizers are preferred in an amount of 0.05 to 0.6% by weight, in particular 0.15 to 0.3% by weight and with a molar mass of more than 500 g / mol.
  • Pentaerythrityl tetrakis-3- (3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate or 1,3,5-trimethyl-2,4,6-tris (3,5-di-tertiary-butyl-4-hydroxybenzyl) benzene are particularly advantageous. Mixtures of these hydrolysis stabilizers can also be used.
  • the yellowness index of the film is not adversely affected in terms of the measurement accuracy compared to a film that has not been equipped, that there are no outgassings, no nozzle deposits, no frame evaporation during film production, which means that the film has an excellent appearance and an excellent profile and
  • the flame-retardant film has excellent flatness, is characterized by excellent stretchability, so that it can be produced reliably and reliably on high speed film lines up to speeds of 420 m / min. Such a film is also economically viable.
  • the regrind can also be used again without adversely affecting the yellowness index of the film.
  • the flame retardant is preferably contained in the non-sealable cover layer C.
  • the base layer B and / or the sealable cover layer A and any intermediate layers which may be present can also be equipped with flame retardants, if required.
  • Fire protection tests according to DIN 4102 and the UL test have shown that in the case of a three-layer film it is sufficient to provide the preferably 0.3 to 2.5 ⁇ m thick top layers with flame retardants in order to achieve sufficient flame retardancy.
  • the flame-retardant, multilayer films produced using the known coextrusion technology become economically interesting in comparison to the monofilms completely finished in high concentrations, since significantly less flame retardants are required.
  • the flame-retardant film can be produced in the dryer without adhesive, preferably by means of masterbatch technology, a suitable predrying or pre-crystallization of the masterbatch and by using low concentrations of hydrolysis stabilizer. Furthermore, no outgassing and deposits were found in the production process.
  • the film according to the invention can be easily recycled without environmental pollution and without loss of mechanical properties, which makes it suitable, for example, for use as short-lived advertising signs, for trade fair construction and for other promotional items where fire protection is required.
  • films according to the invention in the thickness range 5-300 ⁇ m already meet the requirements of building material classes B2 and B1 according to DIN 4102 and UL test 94.
  • the flame retardant is preferably added using masterbatch technology.
  • the flame retardant is dispersed in a carrier material.
  • the carrier material used is the polyester used or other polymers which are compatible with it.
  • the grain size and the bulk density of the masterbatch is similar to the grain size and the bulk density of the thermoplastic, so that a homogeneous distribution and thus a homogeneous flame retardancy can be generated.
  • the masterbatch which contains the flame retardant and optionally the hydrolysis stabilizer, is pre-crystallized or pre-dried.
  • This predrying involves gradual heating of the masterbatch under reduced pressure (20 to 80 mbar, preferably 30 to 60 mbar, in particular 40 to 50 mbar) and with stirring and optionally post-drying at a constant, elevated temperature, likewise under reduced pressure.
  • the masterbatch is preferably at room temperature from a metering container in the desired mixture together with the polymers of the base and / or cover layers and if necessary, other raw material components in batches in a vacuum dryer which, in the course of the drying or dwell time, runs through a temperature spectrum of 10 ° C.
  • the raw material mixture is stirred at 10 to 70 rpm, preferably 15 to 65 rpm, in particular 20 to 60 rpm.
  • the raw material mixture pre-crystallized or pre-dried in this way is in a downstream likewise evacuated container at 90 to 180 ° C., preferably 100 ° C. to 170 ° C., in particular 110 ° C. to 160 ° C. for 2 to 8 hours, preferably 3 to 7 hours, especially dried for 4 to 6 hours.
  • the base layer B and any intermediate layers which are present can additionally contain conventional additives, such as, for example, stabilizers and / or antiblocking agents.
  • the two cover layers A and C additionally contain customary additives, such as stabilizers and / or antiblocking agents. They are expediently added to the polymer or the polymer mixture before the melting. For example, phosphorus compounds such as phosphoric acid or phosphoric acid esters are used as stabilizers.
  • Suitable antiblocking agents are inorganic and / or organic particles, for example calcium carbonate, amorphous silica, talc, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, magnesium phosphate, aluminum oxide, LiF, calcium, barium , Zinc or manganese salts of the dicarboxylic acids used, carbon black, titanium dioxide, kaolin or crosslinked polystyrene or acrylate particles.
  • inorganic and / or organic particles for example calcium carbonate, amorphous silica, talc, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, magnesium phosphate, aluminum oxide, LiF, calcium, barium , Zinc or manganese salts of the dicarboxylic acids used, carbon black, titanium dioxide, kaolin or crosslinked polystyrene or acrylate particles.
  • Antiblocking agents or mixtures of antiblocking agents of the same composition but different particle size can be selected.
  • the particles can individual layers in the respective advantageous concentrations, for example as a glycolic dispersion during the polycondensation or via masterbatches during the extrusion.
  • Preferred particles are SiO 2 in colloidal and in chain-like form. These particles are very well integrated into the polymer matrix and only slightly generate vacuoles. Vacuoles generally cause turbidity and should therefore be avoided.
  • the particle diameters of the particles used are not restricted. To solve the problem, however, it has proven useful to have particles with an average primary particle diameter of less than 100 nm, preferably less than 60 nm and particularly preferably less than 50 nm and / or particles with a average primary particle diameter of greater than 1 ⁇ m, preferably greater than 1.5 ⁇ m and particularly preferably greater than 2 ⁇ m. However, these particles described last should not have an average particle diameter that is greater than 5 ⁇ m.
  • the particle concentration in the base layer B becomes 0 to 0.15% by weight, preferably 0 to 0.12% by weight and in particular 0 to 0.10% by weight.
  • the particle diameter of the particles used is in principle not restricted, but particles with an average diameter of greater than 1 ⁇ m are particularly preferred.
  • the film consists of three layers, the base layer B and cover layers A and C applied to both sides of this base layer, the cover layer A being sealable against itself and against the cover layer C.
  • the top layer C preferably has more pigments (ie higher pigment concentration) than the top layer A.
  • the pigment concentration in this top layer C is between 0.1 and 1.0% by weight, advantageously between 0.12 and 0.8% by weight and in particular between 0.15 and 0.6% by weight.
  • the other sealable cover layer A, which is opposite the cover layer C, is less filled with inert pigments.
  • the concentration of the inert particles in layer A is between 0.01 and 0.2% by weight, preferably between 0.015 and 0.15% by weight and in particular between 0.02 and 0.1% by weight.
  • intermediate layers may also be present.
  • This can in turn consist of the polymers described for the base layers. In a particularly preferred embodiment, it consists of the polyester used for the base layer. It can also contain the additives described.
  • the thickness of an intermediate layer is generally greater than 0.3 ⁇ m and is preferably in the range from 0.5 to 15 ⁇ m, in particular in the range from 1.0 to 10 ⁇ m and very particularly preferably in the range from 1.0 to 5 ⁇ m.
  • the thickness of the cover layers A and C is generally greater than 0.1 ⁇ m and is generally in the range from 0.2 to 4.0 ⁇ m, advantageously in the range from 0.2 to 3, 5 ⁇ m, in particular in the range from 0.3 to 3 ⁇ m and very particularly preferably in the range from 0.3 to 2.5 ⁇ m, it being possible for the outer layers A and C to be of the same or different thickness.
  • the total thickness of the polyester film according to the invention can vary within wide limits. It is preferably 3 to 80 ⁇ m, in particular 4 to 50 ⁇ m, particularly preferably 5 to 30 ⁇ m, layer B having a share of preferably 5 to 90% of the total thickness.
  • the polymers for the base layer B and the two outer layers A and C are expediently fed separately to three extruders in the film production. Any foreign bodies or impurities that may be present can be filtered off from the polymer melt before extrusion.
  • the melts are then formed into flat melt films in a multi-layer nozzle and layered on top of one another. The multilayer film is then pulled off and solidified with the aid of a cooling roller and, if appropriate, further rollers.
  • the invention thus further relates to a method for producing the polyester film according to the invention by the coextrusion method known per se.
  • the procedure is such that the melts corresponding to the individual layers of the film are co-extruded through a flat die, the film thus obtained is drawn off for solidification on one or more rollers, the film is then biaxially stretched (oriented), the biaxial stretched film is heat-set and optionally corona or flame treated on the surface layer intended for treatment.
  • the biaxial stretching (orientation) is generally carried out in succession, with the successive biaxial stretching, in which stretching first lengthwise (in the machine direction) and then transversely (perpendicular to the machine direction) being preferred.
  • the polymer or the polymer mixture of the individual layers is compressed and liquefied in an extruder, it being possible for the additives which may have been added to be present in the polymer or in the polymer mixture.
  • the melts are then pressed simultaneously through a flat die (slot die), and the pressed multi-layer
  • the film is drawn off on one or more take-off rolls, where it cools and solidifies.
  • the stretching in the longitudinal direction can be carried out with the aid of two rolls running at different speeds in accordance with the desired stretching ratio.
  • a corresponding tenter frame is generally used for transverse stretching.
  • the temperature at which the stretching is carried out can vary within a relatively wide range and depends on the desired properties of the film.
  • the longitudinal stretching is carried out at approximately 80 to 130 ° C. and the transverse stretching at approximately 80 to 150 ° C.
  • the longitudinal stretching ratio is generally in the range from 2.5: 1 to 6: 1, preferably from 3: 1 to 5.5: 1.
  • the transverse stretching ratio is generally in the range from 3.0: 1 to 5.0: 1, preferably from 3.5: 1 to 4.5: 1.
  • one or both surface (s) of the film can be coated in-line by the known methods.
  • the in-line coating can serve, for example, to improve the adhesion of a metal layer or a possibly applied printing ink, but also to improve the antistatic behavior or the processing behavior.
  • the strength of the film in the direction of thickness is so great that when measuring the seal seam strength, the seal seam is definitely separated and the film does not tear and tear.
  • the essential factors influencing the planar orientation ⁇ p are the process parameters in the longitudinal stretching and in the transverse stretching, and the SV value (standard viscosity) of the raw material used.
  • the process parameters include in particular the stretching ratios in the longitudinal and transverse directions ( ⁇ MD and ⁇ TD ), the stretching temperatures in the longitudinal and transverse directions (T MD and T JQ ), the film web speed and the type of stretching, in particular that in the longitudinal direction of the Machine.
  • the film web speed here is 340 m / min and the SV value (standard viscosity) of the material is approximately 730.
  • LOE Low
  • REP Rapid Elongation Process
  • the temperatures given relate to the respective roll temperatures in the case of longitudinal stretching and to the film temperatures in the case of transverse stretching, which were measured by means of infrared.
  • the film In the subsequent heat setting, the film is held at a temperature of approximately 150 to 250 ° C. for approximately 0.1 to 10 s. The film is then wound up in the usual way. After biaxial stretching, one or both surface (s) of the film are / are preferably corona or flame treated by one of the known methods. The treatment intensity generally produces a surface tension in the range of over 45 mN / m.
  • the film can also be coated.
  • Typical coatings are adhesion-promoting, antistatic, slip-improving or adhesive layers. It is advisable to apply these additional layers to the film via inline coating using aqueous dispersions before the stretching step in the transverse direction.
  • the film according to the invention is notable for excellent sealability, very good stability to UV light, flame retardancy, very good handling and very good processing behavior.
  • the sealable cover layer A seals not only against itself (fin sealing) but also against the non-sealable cover layer C (lap sealing).
  • the lap sealing starting temperature is only shifted upwards by approx. 10 ° C compared to the fin sealing temperature and the sealing seam strength is not deteriorated by more than 0.3 N / 15 mm.
  • the gloss and the haze of the film are improved compared to films according to the prior art.
  • the regenerate can be fed back into the extrusion in a concentration of 20 to 60% by weight, based on the total weight of the film, without the physical properties of the film being negatively influenced ,
  • the film Due to its excellent sealing properties, its very good handling and its very good processing properties, the film is particularly suitable for processing on high-speed machines. In addition, due to its excellent combination of properties, the film is suitable for a variety of different applications, for example for interior cladding, for trade fair construction and trade fair items, as displays, for signs, for protective glazing of machines and vehicles, in the lighting sector, in shop and shelf construction, as promotional items , Lamination medium.
  • the transparent film according to the invention is also suitable for outdoor applications, such as for greenhouses, canopies, external claddings, covers of materials such.
  • Table 1 summarizes the most important film properties according to the invention.
  • the foils were weathered on both sides with the Atlas Ci 65 Weather Ometer from Atlas according to the test specification ISO 4892 on both sides and then tested with regard to the mechanical properties, the discoloration, the surface defects, the haze and the gloss.
  • the standard viscosity SV (DCE) is measured based on DIN 53726 in dichloroacetic acid.
  • the intrinsic viscosity (IV) is calculated from the standard viscosity as follows
  • the sealing start temperature (minimum sealing temperature)
  • HSG / ET heat-sealed samples (sealing seam 20 mm x 100 mm) are produced, whereby the film at different temperatures with the help of two heated sealing jaws with a sealing pressure of 2 bar and a sealing time of 0 , 5 s is sealed.
  • Test strips 15 mm wide were cut from the sealed samples.
  • the T-seal seam strength was measured as in the determination of the seal seam strength.
  • the seal starting temperature is the temperature at which a seal seam strength of at least 0.5 N / 15 mm is achieved.
  • Seal seam strength To determine the seal seam strength, two 15 mm wide strips of film were placed on top of each other and sealed at 130 ° C, a sealing time of 0.5 s and a sealing pressure of 2 bar (device: Brugger type NDS, one-sided heated sealing jaw). The seal seam strength was determined by the T-Peel method.
  • the friction was determined according to DIN 53 375.
  • the sliding friction number was measured 14 days after production.
  • the surface tension was determined using the so-called ink method (DIN 53 364).
  • the haze according to wood was determined in accordance with ASTM-D 1003-52, but in order to utilize the optimal measuring range, measurements were taken on four layers of film lying one above the other and a 1 ° slit aperture was used instead of a 4 ° perforated aperture.
  • the gloss was determined in accordance with DIN 67 530.
  • the reflector value was measured as an optical parameter for the surface of a film. Based on the standards ASTM-D 523-78 and ISO 2813, the angle of incidence was set at 20 °. A light beam hits the flat test surface at the set angle of incidence and is reflected or scattered by it. The light rays striking the photoelectronic receiver are displayed as a proportional electrical quantity. The measured value is dimensionless and must be specified with the angle of incidence.
  • the size distribution of elevations on film surfaces is determined using a scanning electron microscope and an image analysis system.
  • the scanning electron microscope XL30 CP from Philips with an integrated image analysis program AnalySIS from Soft-Imaging System is used.
  • foil samples are placed flat on a sample holder. Then they are covered at an angle a with a thin metal layer (e.g. made of silver) Where a is the angle between the sample surface and the direction of propagation of the metal vapor. This oblique vaporization creates a shadow behind the elevation. Since the shadows are not yet electrically conductive, the sample is then vapor-deposited or sputtered with a second metal (for example gold), the second coating hitting the sample surface perpendicularly and therefore no shadows being produced in the second coating.
  • a thin metal layer e.g. made of silver
  • the sample surfaces prepared in this way are imaged in a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the shadows of the elevations are visible due to the material contrast of the metals.
  • the sample is oriented in the SEM so that the shadows run parallel to an image edge.
  • the following conditions are set on the SEM for image acquisition: secondary electron detector, working distance 10 mm, acceleration voltage 10 kV and spot 4.5.
  • the brightness and contrast are set so that all image information is displayed as gray values and the intensity of the background noise is so small that it is not detected as a shadow.
  • the length of the shadows is measured with the image analysis program.
  • the threshold value for shadow detection is placed at the point where the 2nd derivative of the gray value distribution of the image crosses the zero point.
  • the image is smoothed with an NxN filter (size 3, 1 iteration).
  • NxN filter size 3, 1 iteration.
  • the magnification, the frame size and the number of evaluated images are chosen so that a total of 0.36 mm 2 film surface are evaluated.
  • the surveys thus determined are divided into classes in order to become one Frequency distribution to come. The division is made into 0.05 mm wide classes between 0 and 1 mm, whereby the smallest class (0 to 0.05 mm) is not used for further evaluations.
  • the diameters (spread perpendicular to the direction of the shadow) of the surveys are similarly classified into 0.2 mm wide classes from 0 to 10 mm, whereby the smallest class is also used for further evaluation.
  • the principle of the measuring method is based on the air flow between a film side and a smooth silicon wafer plate.
  • the air flows from the environment into an evacuated room, the interface between the film and the silicon wafer plate serving as flow resistance.
  • a round film sample is placed on a silicon wafer plate, in the middle of which a hole ensures the connection to the recipient.
  • the recipient is evacuated to a pressure of less than 0.1 mbar. The time in seconds that the air needs to cause a pressure increase of 56 mbar in the recipient is determined.
  • planar orientation is determined by measuring the refractive indices (n) with the Abbe refractometer. sample preparation
  • Sample size and length 60 to 100 mm sample width: corresponds to prism width of 10 mm
  • the sample to be measured must be cut out of the film, in which the running edge of the sample must exactly match the TD direction.
  • the sample to be measured must be cut out of the film, in which the running edge of the sample must exactly match the MD direction.
  • the refractive index of the mixture must be greater than 1,685.
  • the sample cut out in the TD direction is first placed thereon so that the entire prism surface is covered. With the help of a paper handkerchief, the film is now ironed onto the prism so that the film lies firmly and smoothly. The excess liquid must be sucked off. Then a little of the measuring liquid is dripped onto the film. The second prism is folded down and pressed firmly. Now use the right thumbscrew to turn the display scale until a transition from light to dark can be seen in the viewing window in the range 1, 62 to 1, 68. If the transition from light to dark is not sharp, the colors are brought together using the upper knurled screw so that only a light and a dark zone is visible.
  • the sharp transition line is brought into the intersection of the two (in the eyepiece) diagonal lines with the help of the lower knurled screw.
  • the value now displayed in the measurement scale is read and entered in the measurement log. This is the refractive index in the machine direction n MD .
  • the scale is turned with the lower knurled screw until the visible range between 1, 49 and 1, 50 can be seen.
  • the refractive index is determined in n ⁇ or n z (in the thickness direction of the film). So that the transition, which is only slightly visible, can be seen better, the eyepiece is attached placed a polarizing film. This should be turned until the transition is clearly visible. The same applies as for the determination of n MD .
  • the transition from light to dark is not sharp (colored)
  • the colors are brought together using the upper knurled screw so that a sharp transition can be seen.
  • This sharp transition line is brought into the intersection of the two diagonal lines with the help of the lower knurled screw and the value shown on the scale is read and entered in the table.
  • the strip is turned over and the values for the B side are measured.
  • the values for the A side and the B side are combined to mean refractive values.
  • the surface defects are determined visually.
  • the modulus of elasticity, tensile strength and elongation at break are measured in the longitudinal and transverse directions according to ISO 527-1-2.
  • UV stability is tested according to the test specification ISO 4892 as follows Test device: Atlas Ci 65 Weather Ometer
  • Test conditions ISO 4892, i.e. H. artificial weathering
  • Irradiation time 1000 hours (per side)
  • Xenon lamp inner and outer filter made of borosilicate
  • Irradiation cycles 102 minutes of UV light, then 18 minutes of UV light with water spraying the samples, then again 102 minutes of UV light, etc.
  • the color change of the samples after artificial weathering is measured with a spectrophotometer according to DIN 5033.
  • the yellowness index (YID) is the deviation from the colorlessness in the "yellow” direction and is measured in accordance with DIN 6167. Yellowness indexes (YID) of ⁇ 5 are not visually visible.
  • Fire behavior The fire behavior is determined according to DIN 4102 part 2, building material class B2 and according to DIN 4102 part 1, building material class B1 and according to UL test 94.
  • Polyethylene terephthalate chips (produced by the transesterification process with Mn as transesterification catalyst, Mn concentration: 100 ppm) were heated to 150 ° C. Residual moisture dried below 100 ppm and fed to the extruder for the base layer B together with the specified masterbatches. Chips of polyethylene terephthalate were also fed to the extruder for the non-sealable top layer C together with the specified masterbatches.
  • chips were made from a linear polyester consisting of an amorphous copolyester with 78 mol% ethylene terephthalate and 22 mol% ethylene isophthalate (produced by the transesterification process with Mn as the transesterification catalyst, Mn concentration: 100 ppm).
  • the copolyester was dried at a temperature of 100 ° C. to a residual moisture content of below 200 ppm and fed together with the specified masterbatches to the extruder for the sealable outer layer A.
  • the hydrolysis stabilizer and the flame retardant are metered in in the form of a masterbatch.
  • the masterbatch is composed of 20% by weight of flame retardant, 1% by weight of hydrolysis stabilizer and 79% by weight of polyethylene terephthalate.
  • the hydrolysis stabilizer is pentaerylthrityl-tetrakis-3- (3,5-di-tertiary-butyl-4-hydroxylphenyl) propionate.
  • the flame retardant is dimethylphosphonate (® Armgard P 1045).
  • the masterbatch has a bulk density of 750 kg / m 3 and a softening point of 69 ° C.
  • the UV stabilizer 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) -oxyphenol ( ⁇ Tinuvin 1577) is added in the form of masterbatches.
  • the masterbatches consist of 5% by weight tin and 1 577 as a fuel component and 95% by weight polyethylene terephthalate (for the top layer C), or 95% by weight polyethylene isophthalate (for the top layer A) , together.
  • the 5% by weight Tinuvin 1577 masterbatches are only added to the two thick top layers with 20% by weight using the masterbatch technology.
  • the masterbatches were filled at room temperature from separate dosing containers in a vacuum dryer, which runs through a temperature range from 25 ° C to 130 ° C from the time of filling to the end of the dwell time. During the approx. 4-hour residence time, the mixture of both masterbatches is stirred at 61 rpm. The pre-crystallized or pre-dried mixture of the masterbatches is then dried in the downstream hopper, which is also under vacuum, at 140 ° C. for 4 hours.
  • a transparent three-layer film with ABC structure and a total thickness of 12 ⁇ m was produced by coextrusion and subsequent stepwise orientation in the longitudinal and transverse directions.
  • the thickness of the respective cover layers is shown in Table 2.
  • Cover layer A mixture of: 20.0% by weight UV masterbatch based on polyethylene isophthalate
  • masterbatch which contains flame retardant and hydrolysis stabilizer
  • Top layer C mixture of:
  • Nozzle gap width 2.5 mm
  • the film had the required good sealing properties and shows the desired handling and processing behavior.
  • the foils in this and in all the following examples were weathered on both sides for 1000 hours per side using the Atlas Ci 65 Weather Ometer from Atlas according to the test specification ISO 4892 and then with regard to the mechanical properties, the discoloration, the surface defects, the turbidity and the Gloss checked (see Table 4).
  • the film meets the requirements of building material classes B2 and B1 according to DIN 4102 Part 2 and Part 1.
  • the film passes UL test 94.
  • Example 2 In comparison to Example 1, the cover layer thickness of the sealable layer A was increased from 1.5 to 2.0 ⁇ m. As a result, the sealing properties have improved, in particular the sealing seam strength has become significantly greater.
  • Example 3 In comparison to Example 1, a 20 ⁇ m thick film was now produced.
  • the cover layer thickness of the sealable layer A was 2.5 ⁇ m and that of the non-sealable layer C was 2.0 ⁇ m. This has further improved the sealing properties, in particular the seal seam strength has increased significantly. The handling of the film has tended to improve.
  • the copolymer for the sealable outer layer A was changed. Instead of the amorphous copolyester with 78 mol% ethylene terephthalate and 22 mol% ethylene isophthalate, an amorphous copolyester with 70 mol% ethylene terephthalate and 30 mol% ethylene isophthalate was used.
  • the raw material was processed on a twin-screw extruder with degassing without it having to be pre-dried.
  • the cover layer thickness of the sealable layer A was again 2.5 ⁇ m and that of the non-sealable layer C was 2.0 ⁇ m.
  • the sealing properties have improved as a result, in particular the seal seam strength has become significantly greater.
  • the pigment concentration in the two top layers was slightly increased.
  • Comparative Example 1 In comparison to Example 1, the sealable outer layer A was now not pigmented. The victory properties have improved somewhat as a result, but the handling of the film and the processing behavior have become significantly worse.
  • Example 1 Compared to Example 1, the sealable top layer A has now been pigmented as highly as the non-sealable top layer C. The handling and the processing properties of the film have improved as a result of this measure, but the sealing properties have become significantly worse.
  • the non-sealable top layer C was pigmented significantly less. The handling of the film and the processing behavior of the film has become significantly worse.
  • Example 1 from EP-A 0 035 835 was reworked.
  • the sealing behavior of the film, the handling of the film and the processing behavior of the film are worse than in the examples according to the invention.
  • Packaging machines low manufacturing costs -: tendency to stick to rollers or other mechanical parts, block problems during winding and processing

Landscapes

  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

L'invention concerne des feuilles de polyester coextrudées à orientation biaxiale comportant : une couche de base composée d'au moins 90 % en poids d'un polyester thermoplastique, de préférence de polyéthylène téréphtalate (PET) ; au moins une couche de recouvrement scellable ; une deuxième couche de recouvrement non scellable ; éventuellement d'autres couches intermédiaires ; au moins un absorbeur UV, de préférence des hydroxybenzotriazoles et des triazines, et au moins un agent ignifuge, de préférence des composés de phosphore organiques. Lesdites feuilles sont difficilement inflammables, elles présentent une haute stabilité aux UV, elles n'ont pas tendance à être fragilisées par des sollicitations thermiques, leur surface est exempte de voile gênant et elles sont adaptées à de multiples utilisations extérieures et intérieures. Les couches de recouvrement contiennent des agents antiadhérents tels que de l'acide silique, dont les particules ont un diamètre moyen de préférence inférieur à 50 nm et/ou supérieur à 2 νm. La couche de recouvrement scellable est composée de préférence d'un copolyester constitué d'unités d'éthylène téréphtalate et d'éthylène isophtalate.
EP01900408A 2000-02-19 2001-01-10 Feuille de polyester transparente, scellable, traitee pour retarder la combustion et stabilisee aux uv, son procede de fabrication et son utilisation Expired - Lifetime EP1274574B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10007726A DE10007726A1 (de) 2000-02-19 2000-02-19 Transparente, siegelfähige, UV-stabilisierte und flammhemmend ausgerüstete Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10007726 2000-02-19
PCT/EP2001/000207 WO2001060612A1 (fr) 2000-02-19 2001-01-10 Feuille de polyester transparente, scellable, traitee pour retarder la combustion et stabilisee aux uv, son procede de fabrication et son utilisation

Publications (2)

Publication Number Publication Date
EP1274574A1 true EP1274574A1 (fr) 2003-01-15
EP1274574B1 EP1274574B1 (fr) 2008-10-22

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EP01900408A Expired - Lifetime EP1274574B1 (fr) 2000-02-19 2001-01-10 Feuille de polyester transparente, scellable, traitee pour retarder la combustion et stabilisee aux uv, son procede de fabrication et son utilisation

Country Status (6)

Country Link
US (1) US7157132B2 (fr)
EP (1) EP1274574B1 (fr)
JP (1) JP2003522659A (fr)
KR (1) KR20020072582A (fr)
DE (2) DE10007726A1 (fr)
WO (1) WO2001060612A1 (fr)

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Also Published As

Publication number Publication date
JP2003522659A (ja) 2003-07-29
WO2001060612A1 (fr) 2001-08-23
US7157132B2 (en) 2007-01-02
US20030054169A1 (en) 2003-03-20
DE10007726A1 (de) 2001-08-23
EP1274574B1 (fr) 2008-10-22
DE50114441D1 (de) 2008-12-04
KR20020072582A (ko) 2002-09-16

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